Light-sensitive silver halide photographic emulsions containing yellow couplers

ABSTRACT

NEW COMPOUNDS OF THE GENERAL FORMULA   1-(X-CO-CH(-A)-CO-NH-),2-(Y,Z-PHENOXY-),5-(R1-OOC-)BENZENE   WHEREIN X IS-C(CH3)3 OR   W-PHENYL-   W IS HYDROGEN, C6-18 ACYLAMINO, LOWER ALKOXY, HALOGEN OR LOWER ALKYL;   R1 IS AN ALIPHATIC HYDROCARBON RADICAL HAVING 1-18 CARBON ATOMS; Y AND Z ARE EACH HYDROGEN, HALOGEN, LOWER ALKOXY, LOWER ALKYL OR-COOR2; A IS HYDROGEN, HALOGEN OR-OCOR3; R2 AND R3 ARE EACH LOWER ALKYL   ARE FOUND TO BE USEFUL AS YELLOW-FORMING COLOR COUPLERS OF THE PROTECTED TYPE IN LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC EMULSIONS. THESE COMPOUNDS CAN BE SYNTHESIZED FROM READILY AVAILABLE STARTING MATERIALS WITH EASE AND AT CHEAP COST.

United P ten LIGHT-SENSITIVE SILVER HALIDE '-PHOTO- GRAPHIC EMULSIONS CONTAINING YELLOW COUPLERS Masakuni Iwama, Isaburo Inoue, Teruo Hauzawa, Kenro Sakamoto; and Takaya Endo, Tokyo, Japan, assignors to 'Kouishiroku Photo Industry Co., -Ltd., Tokyo, Japan No'Drawing. Filed Dec. 12, 1969, Ser..No. 884,751

1m. 01. G03c 1/40 U.S. 01. 96-100 v 1 Claims ABS TRACT or rrm nrscLosunn New compounds of the general formula wherein X is --C(CH or W is hydrogen, C acylamino, lower alkoxyr halogen or lower al-kyl; I R is an aliphatic hydrocarbonvradicalhaving11-18 car:-

, bon atoms; Y and Z are. each hydrogen, halogen, lower 'alkoxy, lower alkyl or -CQQI A' is hydrogen, halogen or -.OCOR R and R are each lower alkyl are found to be-useful as yellow-forming color couplers of the protected type in light-sensitive silver halide photographic emulsions. These compounds can be synthesized from readily available starting materials with ease and at cheapcost.

This invention relates to a light-sensitive color photographic emulsion, more particularly, to a light-sensitive color'photographic emulsion containing a yellowcoupler of the formula given hereinafter as'a so-called protected 1 type coupler. a I

- uX-oooH-ooHN- halogen, lower alkoxy, lower "A number of compounds have heretofore been pro posedas yellow couplers usedas protected type couplers which are dispersed in a photographic emulsion as a solution in high boiling solvent. 'Very few are found, however, which can be prepared at a low price and in high Patented June 13, 1972 purity. For example, a very expensive starting material must be used for the production of the coupler of the formula tc,n,, -ocmooNn pen,

I tCsHu boomoonnQ which is disclosed in U.S. Pat. 2,875,057. The above known coupler has good solubility in a high boiling solvent but is liable to cause separation in the emulsion under high concentration conditions because the melting point thereof is relatively high. Further, the coupler of the formula) Q-ooomo omnQ which is disclosed in Japanese patent publ. No. 5,5'82/ 1967 gives a less transparent dye image and also tends to separate in the emulsion under high concentration conditions though its melting point is lower than that of the above coupler of U .8. Pat. 2,875,057.

Thus, it has long been desired to find a coupler which can be prepared at a reasonable price and have good solubility in high boiling solvents without causing any separation in a. photographic emplsion. Under the circumstances, we have found that the yellow coupler of the afore-mentioned formula is very advantageous as the protected type coupler.

The novel coupler is readily soluble in a high boiling solvent such as dibutyl phthalate, tricresyl phosphate, etc.

and does not cause any separation in the photographic= emulsion even at high concentration.

Further, the new coupler has a low melting point and accordingly is free from crystallization in the emulsion or even in a dried coating on a support. Moreover, a dye image obtained from the coupler has good spectral absorption characteristics and high transparency. The dye image has further advantages that it is fast to light,

heat and humidity. Thus, the novel coupler which is free from the foregoing disadvantages of the prior couplers is particularly useful as a protected type coupler. The above advantageous characteristics of the novel coupler are considered attributed to an aryloxy group and an 'alkoxycarbonyl group introduced at the 2- and 5-p0sitions, respectively, of the anilide moiety.

Typical couplers included in the general formula given hereinbefore are exemplified below. It should be noted that couplers usable in the invention are not limited only to these compounds.

. I -ooomoonN COOCHHZB (oily; Ref. Index D320 1.5628) (m.p. Mil-141 C GOOCH;

CwHarCOHN-Q-OOCHzOONH C O (His l c OCHEC 0 NH @wocrnconn C 00 012E215 y) (m.p. 128-129 C.)

rnco+-co CHzC OHN HmC o o onzoonN m.D.72-73C.)

Y Synthesis oi theyellow coupler may be made," in gen eral, by condensing an aniline having an aryloxy group and alkoxycarbo'nyl' group "at'the' 2-' andiPositionss spectively, to the amino group with a fl-keto acid ester in an inert solvent or by condensing an aminobenzoylaceh eral formula, the coupler is dissolved in a high-boilingsolvent having a boiling point of ,175 9 C. or higher, such as tricresyl phosphate; di'butyl phthalate andthe like, or a low boiling solvent such as butyl acetate, butyl propionate and the like. on occasion, the'coupler may be dis-,

solved' in a mixture of the above solvents. The resulting solution is mixed with an aqueous gelatine solution containing a surface active .agent. The mixture is emulsified in a high speed rotary mixer or colloid mill and then immediately added to a light-sensitive silver halide photographic emulsion. The photographic emulsion thus treated is coated on a support such a [film base or baryta paper and dried to remove a major part of the low boiling solvent. Alternatively, the emulsified mixture is previously set by cooling, extruded in noodle formand freed from the low boiling solvent by, for example, washing with water, and thereafter added with warming to the photographic emulsion, which is then treated in a similar manner as described above to give a light-sensitive color photographic material. This preparation of photographic material is not limited to the above method but any other modification may be practicable.

The coupler is preferably added to the photographic emulsion in an amount vof 10 10Q' g. per mol of a silver halide contained in the emulsion. The above range is not,

however, critical. The photographic emulsion used in this invention may contain any silver salt such as silver chloride, silver iodide and silver bromoio'dide; Further, the emulsion may be sensitized with a chemical sensitizer, for example, sulfur sensitizer, natural sensitizer found in gelatine, reducing sensitizer and noble metal salt sensitizer. Said photographic emulsion may further contain photographic additives ordinarily used, such as anti-fog gants, stabilizers, anti-stain agents, anti-irradiation agents,

" polymeric modifiers, coating aids, etc. As the optical sensitizer used irrthe photographic emulsion, any known carbocyanine dye or merocyanine dye maybe used.

, The light-sensitive photographic'inaterial thus obtained is then exposed to light and thereafter'treated with a- Typical developing agents used in this invention for the. treatment of light-sensitive photographic material are sul-.

fates, sulfites and hydrochlorides of the following compounds: 1

N,N-diethyl-p-phenylenediamine,"

N-ethyl-n-p-methanesulfonamidoethyl-3:methyl-4-= 7 aminoaniline,

N-ethyl N=hydroxyethyl-p-phenylenediamine,

N-ethyl-N-hydroxyethyl-2-methyl-p-phenylenediamine, l

N,N-diethyl-2-methyl-p-phenylenediaminei Y e As shown by the Table 1- 'givenhereinafter, the novel I coupler used in this invention, whichv is substituted at the 2- and 5-positions in the anilide moiety with an aryloxy group and an .alkoxycarbonyl group, respectively, has a" lower melting point than known couplers. r

TABLE 1 Melting I Point Formula Novel coupler 0 9698 CuHzaCONH-C} l l I C O 0 C2H5 I O 0 CH2 0 ONHT o o o 05H. 7

Known coupler (cf. United 126 127 States Patent 2, 875, 057). tC5Hu 0 CH: C ONH- O C H;

-| tCsH ooomooNH- Known coupler (cf. Japanese CnHzaC 0 110 Patent Publication No. v

/NCH;CH C ONH- 04H!) ooomoorm-Q ed to 20 C. for 10 minutes with a developing solution of the following formulation:

G. N,-N-diethyl-p-phenylenediamine hydrochloride 2.5 Anhydrous sodium sulfite 2.0 Sodium carbonate monohydrate 82.0 Potassium bromide 2.0

Water to make up 1000 ml.

The developed film is subjected to ordinary stopping and fixing and then, after washing with water for 10-15 min- TABLE 2 Required dibutyl phthalate Formula (mL) Novel coupler (5) 0@ 2. 0

CuHzaC ON H- I I C O O C 211 00 01120 ONH C O O C2115 Known coupler (cf. United 7. 5

States Patent 2,875,057). tCsH I GO CHzC ONH- As evidently shown in the foregoing Tables 1 and 2, the novel coupler used in this inventionmelts at a lower temperature audhas better solubility in a high boiling solvent that known couplersand therefore it will be understood that use of the new coupler results in an increase EXAMPLE 1 20 g.'of the foregoing couple (1) is dissolved at 60 C. in a mixture of 20 ml. of dibutyl phthalatc and 60 ml. of butyl acetate. The resulting solution is mixed with 10 ml. of an aqueous solution of 10% Alkanol B (alkyl naphthalene sulfonate produced by Du Pont, U.S.A.) and 200 ml. of an aqueous 5% gelatin solution. The resulting mixture is treated in a colloid mill. The coupler dispersion thus obtained is added tol kg. of a high speed gelatino-silver iodobromide photographic emulsion, which is then coated on a film base and dried.

The light-sensitive photographic material thus obtained is exposed to light in the ordinary manner and then treatutes, treated for 5 minutes with a bleaching bath of the following formulation:

Potassium ferricyanide l00 Potassium bromide 50 Water to make up 1000 ml.

The film is Washed with water for 5 minutes andfurther treated for 5 minutes in a fixing bath of the following formulation:

Sodium thiosulfate pentahydrate-ZSO g. Water to make up 1000 ml.

The film is washed with water for 20-25 minutes and dried. A brilliant yellow dye image having absorption maximum at 440 my is obtained. This dye image was outstandingly excellent more in transparency than the dye image obtained from the known coupler (II) as aforementioned in the same manner as above.

EXAMPLE 2 1 0 g. of the coupler (5) is dissolved at 50 C. in a mixture of 10 ml. of tricresyl phosphate and 30 ml. of butyl acetate. The resulting solution is mixed with 5 ml. of an aqueous solution of 10% Alkanol B and 800 ml.

treated in a colloid mill. The resulting dispersion is added to 500 g. of a gelatino-silver iodobromide emulsion, x

which is then coated on a film base and dried.

The photographic material thus obtained. is.exposed.to.

light and treated at 20 C. for 10 minutes with a developing solution of the following formulation:

Metal "3.0' Anhydrous sodium sulfite 60.0 Hydroquinone 6.0, Anhydrous sodium carbonate 50.0 Potassium bromide Water to make up. 1000 ml.

After being subjected to ordinary stopping, hardening and water-washing steps, the material is, exposed to white light and then treated at 20 C. for 10 minutes with a developing solution of the following formulation:

. G. N,N-diethyl-p-phenylenediamine hydrochloride 5.0 Anhydrous sodium sulfite Sodium carbonate .vlmonohy ate)- j 82.0.,

Potassium bromide Water to makeup 1000 ml,

The developed material is further Subjected to stopping,

fixing, Water washing and bleaching steps and then washed for 20 minutes with running water. After drying, a highly transparent yellow positive dye image having absorption maximum at 445 m is obtained.

EXAMPLE 3 10 g. of the coupler (9) is dissolved at 50 C. in 20 ml. of dibutyl phthalate. The resulting solution is mixed with 5 m1. of an aqueous solution of Alkanol B and 200 ml. of an aqueous 5% gelatine solution. The mixture is passed through a colloid mill several times to form a dispersion. The resulting dispersion is added to 500g. of

a gelatino-silver chlorobromide emulsion, which is then coated on a baryta paper and dried.

Y What we claim is: 1. A light-sensitive silver halide color photographic -einuls'io'ncharacterized by... inclusion. of. a.-yellow coupler of the general formula I Z :Pooorr-oorm-Q COOR;

W is hydrogen, C -acylamino, lower alkoxy, halogen or lower alkyl;

R is an aliphatie hydrocarbon radical having --1- l8 car- The light-sensitive photographic material thus formed I is exposed to light and then treated at 20 C. for 10 minutes with a developing solution of the following formulation:

N ethyl N hydroxyethyl p phenylenediamine sulfate 2.5

Anhydrous sodium. sulfite. 2H0 Hydroxylamine hydrochloride 1.0

Sodium carbonate (monohydrate) 82.0 Water to make up 1000 ml.

The developed material is then treated with a stopping solution which comprises 1 0 ml. of glacial acetic acid, 3.0 g. of sodium hydroxide and 1000 ml. of Water and immediately thereafter with an acidic hardening fixing solution for 4 minutes. After washing with Water for 10 minutes, the material is subsequently treated at 20 C.

Sodium thiosulfate L 200.0 Water to make up 1000 ml.

The material is washed with water for 20 minutes and then treated-for 8 minutes in a stabilizing bath and dried. A yellow dye image having an absorption maximum at 440-m t and excellent in fastness to light and heat as well as in storability is obtained,

I A is hydrogen, halogen or bonatoms;

Y and-Z are. each hydrogen, halogen. lower alkoxy, lower alkyl or -COOR h I j R; and R are-eachlower alkylp g H I 1 :2. A light-sensitive silver halide; color photographic emulsion as claimed in claim .1, wherein said yellow coupler is one having the following formula I IIII (m.p. 94-95 o.

3. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said yellow coupler is one having the following formula -ooen -oonN I I7 000cm A light-sehsitivej'silver halide color photographic emulsioaas claimed in claim 1, wherein said yellow coupler is'one having the following formula i oooH2o,oNn- 00002115.

A 5 A lightsensitive silver halide color photographic emulsion asclaimed in cla'iml, wherein said yellow coupler is one having the following formula CG ia" H i I i i CHCONH O g V Ce ia I r A} i I oomcolm ooczm oooonr (111.1). sear o.

6. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said yellow coupler is one having the following formula (CHmC C O CHIC OHN 1 0 References Cited UNITED STATES PATENTS 3,409,439 11/1968 Yoshida et a1. 96-400 6/1969 Loria 96-100 J. TRAVIS BROWN, Primary Examiner US. Cl. X:R. 

